Effervescent builder compositions and detergent compositions containing the same



United States Patent 3,394,083 EFFERVESCENT BUILDER COMPOSITIONS AND DETERGENT COMPOSITIONS CON- TAINING THE SAME Chung Yu Shen, Olivette, Mo., assignor to Monsanto Company, a corporation of Delaware No Drawing. Filed Aug. 15, 1963, Ser. No. 302,438 Claims. (Cl. 252-157) This invention pertains to effervescent builder compositions and detergent compositions containing the same and more particularly to effervescent detergent compositions in tablet form.

Dry, solid detergent compositions, that is, compositions containing organic active surface active compounds and inorganic builder compounds as well as in some instances other additives designed to impart special properties to the compositions are well-known and extensively used, including detergent compositions in tablet form. However, in such compositions and particularly such compositions in tablet form, a common problem appears to be in the dissolution of the materials, particularly with respect to the rate of dissolution and the uniformity of dissolution, in such a manner that all of the compounds in the composition are in solution and fulfilling their functions at the proper time in the cleaning operation. In particular, a common problem with respect to detergent compositions in tablet form appear to be their slow rate of dissolution. As can be appreciated, therefore, a builder composition which when incorporated in detergent compositions improves their dissolution in aqueous media would be an advancement in this art.

Therefore, an object of this invention is to provide elfervescent builder compositions which when incorporated in detergent compositions exhibit the ability to improve their rate of dissolution in aqueous media.

Another object of this invention is to provide effervescent detergent compositions which exhibit improved dissolution in aqueous media.

A still further object of this invention is to provide a method for improving the dissolution of detergent compositions in aqueous media by incorporating in the detergent compositions an effervescent builder composition.

A stiIl further object of this invention is to provide effervescent builder compositions which when incorporated in dry, solid detergent compositions exhibit the ability to improve their rate of dissolution in aqueous media.

A still further object of this invention is to provide dry, solid effervescent detergent compositions, particularly in tablet form, which exhibit improved dissolution in aqueous media.

A still further object of this invention is to provide a method for improving the dissolution of dry, solid detergent compositions in aqueous media by incorporating in the detergent compositions an effervescent builder composition.

These and other objects will become apparent from a reading of the following detailed description.

The effervescent builder composition of the present invention comprises an admixture of a carbonate containing material and a Water-soluble polyphosphonic acid compound having the following formula OM n wherein n is an integer from 2 to 3 inclusive, M is a member selected from the group consisting of hydrogen and cations with at least 2 of the members being hydrogen when n is 2 and at least 4 of the members being hydrogen 3,394,083 Patented July 23, 1968 when n is 3, and Z is a connecting radical equal in valence to n and containing not more than about 12 atoms, exclusive of hydrogen, in chemical combination. The chemical nature of the connecting radical is relatively unimportant and can include such radicals; as hydrocarbyl radicals, hydrocarbyl substituted amine radicals, hydrocarbyloxy radicals and the like. Preferably Z is an alkylidene radical, a dialkylidene amine radical or a trialkylidene amine radical and especially an alkylidene radical or a trialkylidene amine radical. Especially preferred are the connecting radicals wherein the alkylidene radical contains about 9 carbon atoms or less and more especially preferred for the alkylidene amine radicals are the symmetrical alkylidene amine radicals. In addition, the term cation means, as used herein, the alkali metal ions, ammonium ions and amine ions. The polyphosphonic acid compounds are excellent builders in synthetic organic active detergent compositions, especially organic actives of the anionic, non-ionic and amphoteric types, and are stable and inert in the presence of carbonate materials, particularly alkaline carbonate materials such as alkali metal carbonate materials. In addition, the alkali metal carbonate materials impart some building action to synthetic organic active detergents. The merit of the builder composition of the present invention lies in that although the dry ingredients are normally stable and free flowing, when contacted with sufficient water a reaction takes place with liberation of carbon dioxide which aids the dissolution of the builder composition in aqueous media by disintegrating the composition. This action also aids the dissolution of the other materials present in the detergent compositions, thus enabling a more rapid and uniform dissolution rate.

Of the polyphosphonic acids, the amino tri(lower alkylidene phosphonic acids) as well as their water-soluble acid salts and the lower alkylidene diphosphonic acids as well as their water-soluble acid salts are preferred.

The amino tri(lower alkylidene phosphonic acids) have the following formula wherein X and Y are members selected from the group consisting of hydrogen and lower alkyl (1-4 carbon atoms).

The lower alkylidene diphosphonic acids have the following formula wherein X is a member selected from the group consisting of hydrogen and lower alkyl (l-4 carbon atoms) and Y is a member selected from the group consisting of hydrogen, hydroxyl and lower alkyl (14 carbon atoms).

Amino tri(lower alkylidene phosphonic acid) compounds illustrative of the invention include:

(1) amino tri(methylene phosphonic acid) (2) amino tri(ethylidene phosphonic acid) (3) amino tri(isopropylidene phosphonic acid) (4) amino di(methylene phosphonic acid) mono(ethylelene phosphonic acid) (5) amino di(methylene phosphonic acid) mono(isopropylidene phosphonic acid) (6) amino mono(methylene phosphonic acid) di(ethylidene phosphonic acid) (7) amino mono(methylene phosphonic acid) di(isopropylidene phosphonic acid).

Lower alkylidene diphosphonic acid compounds illustrative of the invention include:

(1) methylene diphosphonic acid (2) ethylidene diphosphonic acid (3) isopropylidene diphosphonic acid (4) l-hydroxy, ethylidene diphosphonic acid (5) l-hydroxy, propylidene diphosphonic acid (6) butylidene diphosphonic acid.

The amino tri(lower alkylidene phosphonic acids), as well as their acid salts, may be prepared by various means, one of which comprises as a first step the preparation of the corresponding ester by the following general reaction:

wherein X and Y are the same as in the foregoing general Formula 2 and R represents an alkyl group.

The free amino tri(lower alkylidene phosphonic acids) and their acid salts may be prepared by hydrolysis of the ester using strong mineral acids such as hydrochloric acid and the like.

The lower alkylidene diphosphonic acids and their acid salts may be prepared by various means, one of which comprises as a first step the preparation of the corresponding ester by the following general reactions:

(1) For the alkylidene diphosphonic acids and their acid salts.

O [I] ZKmetallic CH P(OR)2 2 Xylene (2) For the methylene diphosphonic acid and its acid salts.

P(OR) |ClCH P(O) (OR) CH [P(O) (OR) +RCl (3) For the l-hydroxy alkylidene diphosphonic acids and their acid salts. )Z+ )2 wherein X and Y are the same as in the foregoing general Formula 3 and R represents an alkyl group.

The free lower alkylidene diphosphonic acids and their acid salts may be prepared by hydrolysis of the ester using strong mineral acids such as hydrochloric acid and the like.

The carbonate containing materials which may, in general, be employed in practicing the present invention are the compounds containing essentially carbonate which are capable of reacting with the polyphosphonic acid compounds with the release of carbon dioxide when contacted with sufficient water. In particular are the water-soluble carbonate materials, particularly the inorganic carbonates, and more particularly the alkali metal carbonate materials, such as, sodium carbonate, sodium bicarbonate, sodium sesquicarbonate, potassium carbonate, potassium bicarbonate, lithium carbonate, lithium bicarbonate, ammonium carbonate, ammonium bicarbonate, ammonium sesquicarbonate, and the like including mixtures of these. Ammonia is included herein as an alkali metal in view of the fact that the ammonium salts exhibit substantially the same chemical properties as the alkali metal salts such as the sodium salts and potassium salts. Although the alkali metal carbonates of cesium, rubidium and francium can, in some cases, be used as the carbonate material in practicing the instant invention, since they are relatively expensive and not readily available they are not believed to offer the advantages for use as the foregoing alkali metal carbonates. Because the sodium, potassium and ammonium carbonates are, in general, the most widely used carbonates and because such carbonates are relatively inexpensive as well as being readily available, they are the preferred alkali metal carbonates.

Although the polyphosphonic acid compounds are preferred for use in the eflervescent builder compositions, any water-soluble acid salt of the phosphonic acid compounds may, in general, be employed in practicing the present invention. Of the acid salts of the amino tri(lower alkylidene phosphonic acid) and the lower alkylidene diphosphonic acid compounds, the di-metal salts are preferred, especially the dialkali metal salts, and in particular, the disodium salts, although the other alkali metal salts, such as potassium, lithium and the like, as well as mixtures of the alkali metal salts, may be substituted therefor. Other water-soluble acid salts which may be employed in practicing the present invention include the ammonium salts and amine salts, particularly when the amine is a low molecular weight amine, i.e., having a molecular weight below about 200, and more particularly the alkyl amines, alkylene amines, and alkanolamines containing not more than 2 amine groups. In general, the acid salts may be prepared by neutralizing the polyphosphonic acid compounds with a base that contains essentially the desired cation. For example, to prepare a dissodium salt, one of the polyphosphonic acid compounds can be neutralized with a stoichiometric amount of a base containing the sodium cation, such as NaOH, Na CO and the like.

In general, the carbonate containing materials and the polyphosphonic acid compounds may 'be used in any proportion to form the effervescent builder compositions of the present invention, however, amounts of between about 1:100 and :1 on a weight basis are usually sufflcient in some instances, although amounts of between about 1:10 and 10:1 on a weight basis are preferred.

The polyphosphonic acid compounds of the present invention are good builders in detergent compositions and have the added advantages of being stable, dry, free-flowing compounds which are relatively water-soluble and are hydrolytically stable, that is, resistant to hydrolysis or degradation under various pH and temperature conditions. When the preferred carbonate material is used, i.e., the alkali metal carbonate material, it also imparts some building action to the synthetic organic active detergents. Thus, the effervescent builder material is comprised of materials which are not only capable of effervescing in water with all the advantages inherent therein, but can also function as a builder, that is, as an aid to the organic detergent active in its cleansing action.

The following examples are presented for illustrative purposes with parts by weight being given unless otherwise indicated.

Example 1 Into a conventional Z-necked, 3-liter flask fitted with a reflux condenser, stirrer and thermometer are added about 600 parts of diethyl phosphite and about 127.5 parts of 29% aqueous ammonia solution. The flask is placed in an ice bath and after the mixture becomes cooled to about 0 C. about 325 parts of 37% aqueous formaldehyde solution are added. The flask is removed from the ice bath and heated with the reaction occurring at about 100 C. After the reaction is completed the flask is allowed to cool to room temperature and the reaction products are extracted with benzene and separated by fractional distillation. Hexaethyl aminotri(methylphospho nate) distills between -200 C. at a pressure of .1 mm. and is obtained in a quantity of about 184 parts. The following are the results to enable a comparison between the calculated percent constituents and found percent constituents:

Calculated: 36.78% C, 7.30% H, 3.53% N, 20.01% P. Found: 38.54% C, 7.76% H, 3.00% N, 19.89% P.

The free acid, laminotri(methylphosphonic acid),

is prepared by hydrolysis of a portion of the foregoing prepared ester. In a flask similar to that described above 40 grams of the ester is refluxed with about 200 ml. of concentrated hydrochloric acid for a period of about 24 hours. The free acid, a sirupy liquid, crystallizes on prolonged standing (about 1 week) in a desiccator. The yield is 20 grams. The equivalent weight of the free acid, by titration, is found to be 62 as compared with the calculated value of 59.8.

Example 2 In a reaction vessel about 299 parts of amino tri(methylene phosphonic acid) are added to about 800 parts of a 10% by weight sodium hydroxide solution and the resultiug reaction product evaporated to dryness at about 130 C. The resulting product is disodium amino tri(methylene phosphonate).

Example 3 Into a reaction vessel are charged about 18.6 parts of diethyl chloromethylphosphonate and about 32.2 parts of triethyl phosphite. This mixture is stirred and heated to reflux. A bubbler attached to the otherwise closed systern checks the ethyl chloride evolution. At 160 C. the ethyl chloride comes off at a steady rate. After 17 hours of refluxing the temperature reaches about 220 C. and the gas evolution becomes quite slow. The mixture is cooled to room temperature and vacuum distilled. The tetraethyl methylenediphosphonate boils lat 1289/.9 mm. with a yield of 77% based on the diethyl chloromethylphosphona-te reactant. The free acid, methylene diphosphonic acid, H C(P(O)(OH) is prepared by hydrolysis of a portion of the foregoing, prepared ester. In a flask similar to that described above 80 grams of the ester is refluxed with about 400 ml. of concentrated hydrochloric acid for a period of about 24 hours. The free acid, a sirupy liquid, crystallizes on prolonged standing (about 1 week) in a desiccator.

Example 4 In a reaction vessel about 178 parts of methylene diphosphonic acid are added to about 800 parts of a 10% by weight sodium hydroxide solution and the resulting reaction product evaporated to dryness at about 130 C. The resulting product is disodium methylene diphosphonate.

Example 5 Into a reaction vessel are charged about 60 parts of diethyl acetyl phosphonate and about 46 parts of diethyl phosphonate and treated with a catalytic amount of sodi- Example 6 In a reaction vessel about 209 parts of l-hydroxy ethylidene diphosphonic acid are added to about 800 parts of a 10% by weight of sodium hydroxide solution and the resulting reaction product evaporated to dryness at about 130 C. The resulting product is disodium l-hydroxy, ethylidene diphosphonate.

As previously mentioned, the improved builder may be used with any of the conventional detergents classed as synthetic anionic, nonionic and/or amphoteric surface active compounds which are suitable as cleansing agents. Anionic surface active compounds can be broadly described as compounds which contain hydrophilic and lyophilic groups in their molecular structure and which ionize in an aqueous medium to give anions containing the lyophilic group. These compounds are usually the alkali metal salts of organic sulfonates or sulfates, particularly the sodium salts, such as alkyl aryl sulfonates (e.g. sodium dodecyl benzene sulfonates), sulfate of straight chain primary alcohols (e.g., sodium lauryl sulfate) and the like. Nonionic surface active compounds can be broadly described as compounds which do not ionize but acquire hydrophilic characteristics from an oxygenated side chain, usually polyoxyethylene, while the lyophilic part of the molecule may come from fatty acids, phenols, alcohols, amides or amines. For example purposes only, the polyethylene oxide condensates of alkyl phenols (e.g., condensation product formed from 1 mole nonyl phenol and 10 moles ethylene oxide), the condensation products of aliphatic alcohols and ethylene oxide (e.g., condensation product formed from 1 mole tridecanol and 12 moles ethylene oxide) are suitable nonionic surface active compounds in practicing the invention. Amphoteric surface active compounds can be broadly described as compounds which have both anionic and cationic groups in the same molecule. Examples of such compounds includes sodium Namethyl taurate and sodium N-coco beta amino propinate. Although the preferred organic actives for formulation purposes are dry, solid materials, liquid organic actives can be employed if they do not contain water in sufficient amounts to initiate the effervescent builder composition reaction.

The amount of effervescent builder composition necessary to be used with the surface active compound (active) may vary depending upon, inter alia, the end use, type of active employed, pH conditions and the like. It should also be noted that the builder of the instant invention may be used in conjunction with the conventional polyphosphate builders. For example, a builder containing a ratio by weight of sodium tripolyphosphate and the eifervescent builder composition with 1:10 and 10:1 functions, in some instances, better as a builder than either when used individually. The new builders can be employed with detergents as above described in any desired proportions. The optimum active/ builder ratio depends upon the particular active employed and the end use for which the mixture is intended but most generally will fall within the range of an active/builder weight ratio 4:1 to 1:4, which is, therefore, the preferred range to practice the invention.

The resulting efiervescent detergent composition, that is, the active and the effervescent builder composition, of the present invention is generally effective when used in aqueous systems in conventional amounts such as is normally used with detergent compositions containing known builders (e.g., polyphosphates) and which is generally about .2% concentration or below.

The invention is not to be limited to any particular method of mixing the builder composition and the organic detergent active. The builder may be mechanically mixed in, slurried with, or dissolved in the detergent active. In addition, the builder composition may be admixed with the organic detergent active as well as being added simultaneously or separately to an aqueous solution. In any event, the builder composition is intended to be used with the organic active detergent active at the time of application as a cleansing agent.

A preferred embodiment of the detergent composition of the present invention is an effervescent detergent tablet. The tablet may be prepared by various methods such as, compacting the dry, free-flowing detergent composition in a suitable mold under sufficient pressure in order for the tablet to retain its shape and have sufficient surface and internal strength to withstand ordinary handling and packaging without fracturing or crumbling. Usually pressures in excess of about 25 lbs/sq. in, are suitable and, in general, the pressures need not be in excess of about 800 lbs/sq. in., although pressures in excess may in some instances be used. The detergent tablets of the present invention may be made of various shapes and sizes depending upon the purpose for which they are to be used.

In order to illustrate the effect which the effervescent builder composition has on the dissolution rate of a nonionic-type detergent tablet as compared with this type tablet containing sodium tripolyphosphate as the builder the following comparison was made. A nonionic-type detergent tablet, i.e., about 1% diameter by /2" height weighing about 19 grams, formulated as follows was prepared.

Additive: Percent by weight Sodium tripolyphosphate 30 Sodium sulfate 15 Alkyl phenol-E condensate nonionic surfactant Sodium silicate solution (40% solids) Builder 1 30 1 Efierveseent builder composition: 15% by weight NauQm and 15% by weight of amino tri(methylene phosphonic acid) or 30% sodium tripolyphosphate.

When the tablet containing the effervescent builder composition was dropped into water of about C. and of a sufficient amount to provide a concentration of detergent composition conventionally used for cleansing purposes, the tablet disintegrated, dispersed and went into solution in less than 2 minutes. When the tablet containing the widely used builder, sodium tripolyphosphate, was dropped into a like amount of water, the tablet took over 4 minutes to disintegrate, disperse and go into solution. As can be appreciated, a detergent composition, particularly in tablet form, which exhibits a relatively rapid dissolution rate in order for it to effect a rapid and uniform detergent concentration in aqueous media, thus enabling it to begin its cleaning function in a rapid more efficient manner would be an important advantage to such composition.

While a detergent composition in accordance with this invention need contain only a detergent active of the class described and the effervescent builder composition, it will be appreciated that the incorporation in the mixture of additional ingredients commonly used with cleansing agents, such as perfume, anti-redeposition agents (e.g., carboxy-methylcellulose), brightening agents (e.g., fluorescent dyes) and the like, is contemplated as being within the invention.

What is claimed is:

1. A detergent composition consisting essentially of a water soluble, organic, synthetic, active component selected from the group consisting of anionic, nonionic and amphoteric active detergent compounds and an effervescent builder component comprising a stable admixture of a carbonate material selected from the group consisting of alkali metal carbonates and ammonium carbonates, and an amino tri(lower alkylidene phosphonic acid) compound having the formula X o OM I II/ N- i-P Y OM 3 wherein X and Y members selected from the group consisting of hydrogen and lower alkyl containing from 1 to 4 carbon atoms; and M is selected from the group consisting of hydrogen, alkali metal ions, ammonium ion and amine ions of amines having a molecular weight below about 200 and containing no more than 2 amine groups selected from the group consisting of alkyl amines, alkylene amines and alkanol amines, with at least 4 of the members being hydrogen; said builder component and said organic active component are present in amounts of between the weight ratio of 1:4 and 4:1, respectively, and said carbonate material and said amino tri(lower alkylidene phosphonic acid) compound are present in amounts between the weight ratio of 1:10 and 10:1, respectively.

2. The detergent composition of claim 1 wherein said amino tri(lower alkylidene phosphonic acid) compound is amino tri(methylene phosphonic acid).

3. The detergent composition of claim 1 wherein the salt of the amino tri(lower alkylidene phosphonic acid) compound is the dialkali metal salt.

4. The detergent composition of claim 2 wherein said composition is in tablet form.

5. The detergent composition of claim 3 wherein said dialkali metal salt of the amino tri(lower alkylidene phosphonic acid) compound is disodium amino tri (methylene phosphonate).

6. The detergent composition of claim 5 wherein said composition is in tablet form.

7. A detergent composition consisting essentially of a water soluble, organic, synthetic, active component selected from the group consisting of anionic, nonionic and amphoteric active detergent compounds and an effervescent builder component consisting essentially of a stable admixture of a carbonate material selected from the group consisting of alkali metal carbonates and ammonium carbonates and a lower alkylidene diphosphonic acid compound having the formula Wherein X is a member selected from the group consisting of hydrogen and lower alkyl containing from 1 to 4 carbon atoms and Y is a member selected from the group consisting of hydrogen, hydroxyl and lower alkyl containing from 1 to 4 carbon atoms and M is selected from the group consisting of hydrogen, alkali metal ions, ammonium ion and amine ions of amines having a molecular weight below about 200 and containing no more than 2 amine groups selected from the group consisting of alkyl amines, alkylene amines and alkanol amines, with at least 2 of the members being hydrogen; said builder component and said organic active component are present in amounts between the weight ratio of 1:4 and 4:1, respectively and said carbonate material and said lower alkylidene diphosphonic acid compound are present in amounts between the weight ratio of 1:10 and 10:1 respectively.

8. The detergent composition of claim 7 wherein said lower alkylidene diphosphonic acid compound is methylene diphosphonic acid.

9. The detergent composition of claim 7, wherein the salt of said lower alkylidene diphosphonic acid is an alkali metal salt and said composition is in tablet form.

10. The detergent composition of claim 7 wherein said lower alkylidene diphosphonic acid compound is l-hydroxy, ethylidene diphosphonic acid.

11. The detergent composition of claim 8 wherein said composition is in tablet form.

12. The detergent composition of claim 9, wherein said alkali metal salt is a sodium salt of methylene diphosphonic acid.

13. The detergent composition of claim 9, wherein said alkali metal salt is a sodium salt of l-hydroxy, ethylidene diphosphonic acid.

14. The detergent composition of claim 10 wherein said composition is in tablet form.

15. The detergent composition consisting essentially of a water soluble, synthetic, organic active detergent component selected from the group consisting of anionic, nonionic, and amphoteric active detergent compounds and an effervescent builder component consisting essentially of a stable admixture of a carbonate material selected from the group consisting of alkali metal carbonates and ammonium carbonates and a polyphosphonic acid compound selected from the group consisting of amino tri (lower alkylidene phosphonic acid) compounds having the formula X o OM N r t 1" \OIU 3 wherein X is selected from the group consisting of hydrogen and lower alkyl containing from 1 to 4 carbon atoms, and Y is selected [from the group consisting of hydrogen, hydroxyl and lower alkyl containing from 1 to 4 carbon atoms, and M is selected from the group consisting of hydrogen, alkali metal ions, ammonium ion, and amine ions of amines having a molecular weight below about 200 and containing no more than 2 amine groups selected from the group consisting of alkyl amines, alkylene amines and alkanol amines, with at least 2 of the members being X 0 OM lhai 1 hydrogen, and mixtures thereof; said builder component and said organic active component are present in the amount between the weight ratio of 1:4 and 4:1 respectively, and said carbonate material and said polyphosphonic acid compound are present in the amount between the weight ratio of 1:100 and :1 respectively.

References Cited UNITED STATES PATENTS 1,450,865 4/1923 Pelc 252-157 2,169,344 8/1939 Kimball 252-152 XR 3,081,267 3/1963 Laskey 252-137 XR 3,122,417 2/1964 Blaser et a1. 252-99 XR 3,149,151 9/1964 Schiefer et a1. 252-99 XR 3,159,581 12/1964 Diehl 252-137 XR 3,213,030 10/1965 Diehl 252-152 3,235,506 2/1966 Diehl et al. 252-152 XR 3,236,592 2/ 1966 Nielson 252-157 XR 3,236,726 2/1966 Rose 252-157 XR FOREIGN PATENTS 934,090 8/1963 Great Britain.

OTHER REFERENCES Petrov et al., Chemi-cal Abstracts, vol. 54 (1960), page 260h.

LEON D. ROSDOL, Primary Examiner.

M. WEINBLATT, Assistant Examiner. 

1. A DETERGENT COMPOSITION CONSISTING ESSENTIALLY OF A WATER SOLUBLE, ORGANIC, SYNTHETIC, ACTIVE COMPONENT SELECTED FROM THE GROUP CONSISTING OF ANIONIC, NONIONIC AND AMPHOTERIC ACTIVE DETERGENT COMPOUNDS AND AN EFFERVESCENT BUILDER COMPONENT COMPRISING A STABLE ADMIXTURE OF A CARBONATE MATERIAL SELECTED FROM THE GROUP CONSISTING OF ALKALI METAL CARBONATES AND AMMONIUM CARBONATES, AND AN AMINO TRI(LOWER ALKYLIDENE PHOSPHONIC ACID) COMPOUND HAVING THE FORMULA 